Surface evolution of thermoelectric material KCu_(4)Se_(3) explored by scanning tunneling microscopy

Novel two-dimensional thermoelectric materials have attracted significant attention in the field of thermoelectric due to their low lattice thermal conductivity.A comprehensive understanding of their microscopic structures is crucial for driving further the optimization of materials properties and developing novel functional materials.Here,by using in situ scanning tunneling microscopy,we report the atomic layer evolution and surface reconstruction on the cleaved thermoelectric material KCu_(4)Se_(3) for the first time.We clearly revealed each atomic layer,including the naturally cleaved K atomic layer,the intermediate Se^(2-)atomic layer,and the Se^(-)atomic layer that emerges in the thermodynamic-stable state.Departing from the maj ority of studies that predominantly concentrate on macroscopic measurements of the charge transport,our results reveal the coexistence of potassium disorder and complex reconstructed patterns of selenium,which potentially influences charge carrier and lattice dynamics.These results provide direct insight into the surface microstructures and evolution of KCu_(4)Se_(3),and shed useful light on designing functional materials with superior performance.

Scanning tunneling microscopic investigation on morphology of magnetic Weyl semimetal YbMnBi2

YbMnBi2 is a recently discovered time-reversal-symmetry breaking type-Ⅱ Weyl semimetal.However, as a representation of the new category of topological matters, the scanning tunneling microcopy(STM) results on such important material are still absent.Here, we report the STM investigations on the morphology of vacuum cleaved single crystalline YbMnBi2 samples.A hill and valley type of topography is observed on the YbMnBi2 surface, which is consistent with the non-layer nature of its crystal structure.Analysis of STM images yields the information of the index of the vicinal surface.Our results here lay a playground of future atomic scale research on YbMnBi2.

The scanning tunneling microscopy and spectroscopy of GaSb_(1-x)Bi_(x) films of a few-nanometer thickness grown by molecular beam epitaxy

The ultrahigh vacuum scanning tunneling microscope(STM)was used to characterize the GaSb_(1-x)Bi_(x) films of a few nanometers thickness grown by the molecular beam epitaxy(MBE)on the GaSb buffer layer of 100 nm with the GaSb(100)substrates.The thickness of the GaSb_(1-x)Bi_(x) layers of the samples are 5 and 10 nm,respectively.For comparison,the GaSb buffer was also characterized and its STM image displays terraces whose surfaces are basically atomically flat and their roughness is generally less than 1 monolayer(ML).The surface of 5 nm GaSb_(1-x)Bi_(x) film reserves the same terraced morphology as the buffer layer.In contrast,the morphology of the 10 nm GaSb_(1-x)Bi_(x) film changes to the mound-like island structures with a height of a few MLs.The result implies the growth mode transition from the two-dimensional mode as displayed by the 5 nm film to the Stranski-Krastinov mode as displayed by the 10 nm film.The statistical analysis with the scanning tunneling spectroscopy(STS)measurements indicates that both the incorporation and the inhomogeneity of Bi atoms increase with the thickness of the GaSb_(1-x)Bi_(x) layer.

SCANNING TUNNELING MICROSCOPY OF （CrFe）7C3

The microstructure of(CrFe)_7C_3 has been studied with scanning tunneling microscopy.It shows that a carbide consists of colonies which are full of stacking faults. The stacking faults in one colony are parallel while those in different colonies lie at angle with each other.

Adsorption behavior of triphenylene on Ru(0001) investigated by scanning tunneling microscopy

As a representative of small aromatic molecules, triphenylene(TP) has markedly high carrier mobility and is an ideal precursor for building graphene nanostructures. We mainly investigated the adsorption behavior of TP molecules on Ru(0001) by using scanning tunneling microscopy(STM). In submonolayer regime, TP molecules are randomly dispersed on Ru(0001) and the TP overlayer can be thoroughly dehydrogenated and converted into graphene islands at 700 K. Due to weak interaction between TP molecules and graphene, the grooves formed among graphene islands have confinement effect on TP molecules. TP adopts a flat-lying adsorption mode and has two adsorption configurations with the 3-fold molecular axis aligned almost parallel or antiparallel to the ■ direction of the substrate. At TP coverages of 0.6 monolayer(ML)and 0.8 ML, the orientational distributions of the two adsorption configurations are equal. At about 1.0 ML, we find the coexistence of locally ordered and disordered phases. The ordered phase includes two sets of different superstructures with the symmetries of ■R23.41° and p(4 × 4), respectively. The adsorption behavior of TP on Ru(0001) can be attributed to the delicate balance between molecule–substrate and molecule–molecule interactions.

Scanning tunneling microscopy study of molecular growth structures of Gd@C_(82) on Cu(111)

The coverage and temperature-dependent nucleation behaviors of the Gd@C82 metallofullerenes on Cu（111） have been studied by low-temperature scanning tunneling microscopy （LT-STM） in detail. Upon molecular deposition at low temperature, Gd@C82 molecules preferentially decorate the steps and nucleate into single layer islands with increasing coverage. Further annealing treatment leads some of the Gd@C82 molecules to assemble into bright and dim patches, which are correlated to the adsorption induced substrate reconstruction. Upon sufficient thermal activation, Gd@C82 molecules sink into the Cu（111） surface one-copper-layer-deep, forming hexagonal close-packed molecular islands with intra-molecular details observed as striped patterns. By considering the commensurability between the Gd@C82 nearest-neighbor distance and the lattice of the underlying Cu（111）, we clearly identified two kinds of in-plane molecular arrangements as （19（1/2）×19（1/2））R23.4°and （19（1/2）×19（1/2））R36.6°with respect to Cu（111）. Within the assembled Gd@C82 molecular, island molecules with dim–bright contrast are spatially distributed, which may be modulated by the preexisted species on Cu（111）.

Electronic phase diagram of NaFe_(1-x)Co_xAs investigated by scanning tunneling microscopy

Our recent scanning tunneling microscopy （STM） studies of the NaFelxCoxAs phase diagram over a wide range of dopings and temperatures are reviewed. Similar to the high-Tc cuprates, the iron-based superconductors lie in close proximity to a magnetically ordered phase. Therefore, it is widely believed that magnetic interactions or fluctuations play an important role in triggering their Cooper pairings. Among the key issues regarding the electronic phase diagram are the properties of the parent spin density wave （SDW） phase and the superconducting （SC） phase, as well as the interplay between them. The NaFe l-xCoxAs is an ideal system for resolving these issues due to its rich electronic phases and the charge-neutral cleaved surface. In our recent work, we directly observed the SDW gap in the parent state, and it exhibits unconventional features that are incompatible with the simple Fermi surface nesting picture. The optimally doped sample has a single SC gap, but in the underdoped regime we directly viewed the microscopic coexistence of the SDW and SC orders, which compete with each other. In the overdoped regime we observed a novel pseudogap-like feature that coexists with supercon- ductivity in the ground state, persists well into the normal state, and shows great spatial variations. The rich electronic structures across the phase diagram of NaFel_xCoxAs revealed here shed important new light for defining microscopic models of the iron-based superconductors. In particular, we argue that both the itinerant electrons and local moments should be considered on an equal footing in a realistic model.

Graphene/Rh(111) Structure Studied Using In-Situ Scanning Tunneling Microscopy

Scanning tunnel microscopy （STM） is performed to verify if an Rh ＇nails＇ structure is formed accompanying the graphene growing during chemical vapor deposition. A structure of a graphene island in an Rh vacancy island is used as the start. While the graphene island is removed by oxygenation, the variations of the Rh vacancy island are imaged with an in-situ high-temperature STM. By fitting with our model and calculations, we conclude that the best fit is obtained for 0% Rh, i.e., for the complete absence of nails below graphene on Rh（111）. That is, when graphene is formed on Rh（111）, the substrate remains fiat and does not develop a SUPPorting nail structure.

Some Unusual Features of Highly Oriented Pyrolytic Graphite Observed by Electrochemical Scanning Tunneling Microscopy

Highly oriented pyrolytic graphite (HOPG) is the substrate often used in scanningtunneling Ancroscopy (STM). It is well known that STM images of the basal plane of HOPG showsome unusual structUral patterns. In this letter, we present in situ STM images of some unusualfeatures on HOPG in solutions, including normal or abnormal chain-like featUres and hexagonal oroblique superPeriodic structures. These features emerge both next to and apart from the step ofHOPG.

Direct Observation of Transition Metal Dichalcogenides in Liquid with Scanning Tunneling Microscopy

We present atomic-resolution images of TiSe2,MoTe2 and TaS2 single crystals in liquid condition using our home-built scanning tunneling microscopy(STM).By facilely cleaving of single crystals in liquid,we were able to keep the fresh surface not oxidized within a few hours.Using the high-stable home-built STM,we have obtained atomic resolution images of TiSe2 accompanied with the single atom defects as well as the triangle defects in solution for the first time.Besides,the superstructure of MoTe2 and hexagonal chargedensity wave domain structure in nearly commensurate phase of TaS2 were also obtained at room temperature(295 K).Our results provide a more efficient method in investigating the lively surface of transition metal dichalcogenides.Besides,the high stable liquid-phase STM will support the further investigations in liquid-phase catalysis or electrochemistry.

Electrochemical Scanning Tunneling Microscopy──An Ex－situ Study of the Growth of Polypyrrole Films on Electrodes

his paper covers the electropolymerized polypyrrole doped with p-toluenesul-fonate studied using scanning tunneling microscope. The growth processes of polypyrrole films on the electrode surface were observed. Polypyrrole chain struc-ture with many separated micro-holes of 0. 15 nm diameter at the initial state ofelectropolymerization can be seen from obtained STM images. This structure is ex-tremely similar to the pioneer-proposed ideal structure of polypyrrole chains. Thereexisted some helical structure and simple strands on the electrode surface, which isdue to different existing states of polypyrrole chains on electrode surface. STM ex-periments showed that polypyrrole chains were firstly formed on the electrode sur-face, then, they growed gradually by 3-dimensional mode during slow oxidation toform many separated micro-islands. Finally, a large corrugation area of polymerfilms occurred on the electrodes.

FABRICATION OF THE TIP FOR ELECTROCHEMICAL SCANNING TUNNELING MICROSCOPY

A nover technique for the fabrication of the tip for e tectrochemical scanning tunneting microscopy(ECSTM)is presented. The curvature radius of the fabricated tip is smatter than 1 μM. Faradaic leakage current is tess than 0.1nA in the sotution of 1 mol/L NaCl. The atomic image of highty oriented pyrotytic graphite (HOPG)has been taken using the prepared tip.

Probing the Majorana bound states in a hybrid nanowire double-quantum-dot system by scanning tunneling microscopy

We propose an interferometer composing of a scanning tunneling microscope(STM),double quantum dots(DQDs),and a semiconductor nanowire carrying Majorana bound states(MBSs)at its ends induced by the proximity effect of an s-wave superconductor,to probe the existence of the MBSs in the dots.Our results show that when the energy levels of DQDs are aligned to the energy of MBSs,the zero-energy spectral functions of DQDs are always equal to 1/2,which indicates the formation of the MBSs in the DQDs and is also responsible for the zero-bias conductance peak.Our findings suggest that the spectral functions of the DQDs may be an excellent and convenient quantity for detecting the formation and stability of the spatially separated MBSs in quantum dots.

SURFACE PRESSURE,SURFACE POTENTIAL AND SCANNING TUNNELING MICROSCOPY STUDIES FOR N-DOCOSYLPYRIDINIUM-TCNQ MONOLAYER

Simultaneous measurements of surface pressure and surface potential and scanning tunneling microscopy study for N-docosylpyridinium- TCNQ monolayer were carried out.These methods allow us to get more informations on properties of the monolayer.The molecules at the final stage of compression are really in compact stack although a voluminous hydrophilic head exists in the molecule.

Molecular Beam Epitaxy Growth and Scanning Tunneling Microscopy Study of Pyrite CuSe2 Films on SrTiO3

We perform molecular beam epitaxy growth and scanning tunneling microscopy study of copper diselenide （CuSe2 ） films on SrTiO3 （001）. Using a Se-rich condition, the single-phase pyrite CuSe2 grows in the Stranski-Krastanov （layer-plus-island） mode with a preferential orientation of （111）. Our careful inspection of both the as-grown and post-annealed CuSe2 films at various temperatures invariably shows a Cu-terminated surface, which, depending on the annealing temperature, reconstructs into two distinct structures 2 ×√3 and √x ×√3-R30°. The Cu termi- nation is supported by the depressed density of states near the Fermi level, measured by in-situ low temperature scanning tunneling spectroscopy. Our study helps understand the preparation and surface chemistry of transition metal pyrite dichalcogenides thin films.

Topography Structure and Scanning Tunneling Spectrum of Nickel( Ⅱ )-tetraphenylporphyrin Molecules on Au(111)

Scanning tunneling microscopy （STM） and scanning tunneling spectroscopy （STS） were performed on monolayer film of NiTPP supported on Au（111） under ultrahigh vacuum （UHV） conditions. The constant current STM images show remarkable bias dependence. High resolution STM data clearly show the individual NiTPP molecules and allow easy differentiation between NiTPP and CoTPP reported before. Scanning tunneling spectra, as a function of molecule-tip separation, were acquired over a range of tip motion of 0.42 nm. Spectra do not show the variation in band splitting with tip distance. It appears for molecules such as NiTPP that the average potential at the molecule is essentially the same at the same metal substrate. For molecules of the height of NiTPP, the scanning tunneling spectra should give reliable occupied and unoccupied orbital energies over a wide range of tip-molecule distances.

Image charge effect on the light emission of rutile TiO2(110) induced by a scanning tunneling microscope

The plasmon-enhanced light emission of rutile TiO2（110） surface has been investigated by a low-temperature scanning tunneling microscope （STM）. We found that the photon emission arises from the inelastic electron tunneling between the STM tip and the conduction band or defect states of TiO2（110）. In contrast to the Au（111） surface, the maximum photon energy as a function of the bias voltage clearly deviates from the linear scaling behavior, suggesting the non-negligible effect of the STM tip on the band structure of TiO2. By performing differential conductance （dl/dV） measurements, it was revealed that such a deviation is not related to the tip-induced band bending, but is attributed to the image charge effect of the metal tip, which significantly shifts the band edges of the TiO2（110） towards the Femi level （EF） during the tunneling process. This work not only sheds new lights onto the understanding of plasmon-enhanced light emission of semiconductor surfaces, but also opens up a new avenue for engineering the plasmon-mediated interfacial charge transfer in molecular and semiconducting materials.

Microscopic growth mechanism and edge states of monolayer 1T'-MoTe_(2)

Transition metal ditellurides(TMTDs)have versatile physical properties,including non-trivial topology,Weyl semimetal states and unique spin texture.Controlled growth of high-quality and large-scale monolayer TMTDs with preferred crystal phases is crucial for their applications.Here,we demonstrate the epitaxial growth of 1T'-MoTe_(2) on Au(111)and graphitized silicon carbide(Gr/SiC)by molecular beam epitaxy(MBE).We investigate the morphology of the grown1T'-MoTe_(2) at the atomic level by scanning tunnelling microscopy(STM)and reveal the corresponding microscopic growth mechanism.It is found that the unique ordered Te structures preferentially deposited on Au(111)regulate the growth of monolayer single crystal 1T'-MoTe_(2),while the Mo clusters were preferentially deposited on the Gr/SiC substrate,which impedes the ordered growth of monolayer MoTe_(2).We confirm that the size of single crystal 1T'-MoTe_(2) grown on Au(111)is nearly two orders of magnitude larger than that on Gr/SiC.By scanning tunnelling spectroscopy(STS),we observe that the STS spectrum of the monolayer 1T'-MoTe_(2) nano-island at the edge is different from that at the interior,which exhibits enhanced conductivity.

Room temperature spontaneous surface condensation of boronic acids observed by scanning tunneling microscopy

Herein,we discovered that the surface-confined condensation of boronic acid can happen spontaneously at room temperature,by comparing the kinetics of condensation of boronic acids with and without the negative sample bias,we found that the negative sample bias indeed accelerates the self-condensation reaction of boronic acid.Combining with in-situ STM images and ultraviolet photoemission spectrum(UPS)analysis,a reversible adsorption mechanism model was proposed and reasonably explains the reversible electric-field-induced phase transformation.

On-Surface Stereochemical Characterization of a Highly Curved Chiral Nanographene by Noncontact Atomic Force Microscopy and Scanning Tunneling Microscopy

A highly distorted chiral nanographene structure composed of triple corannulene-fused[5]helicenes is prepared with the help of the Heck reaction and oxidative photocyclization with an overall isolated yield of 28%.The complex three-dimensional(3D)structure of the bowl-helix hybrid nanostructure is studied by a combination of noncontact atomic force microscopy(AFM)and scanning tunneling microscopy(STM)on the Cu(111)surface,density functional theory calculations,AFM/STM simulations,and high-performance liquid chromatography-electronic circular dichroism analysis.This examination reveals a molecular structure in which the three bowl-shaped corannulene bladesd position themselves in a C3-symmetric fashion around a highly twisted triphenylene core.The molecule appears to be shaped like a propeller in which the concave side of the bowls face away from the connected[5]helicene motif.The chirality of the nanostructure is confirmed by the direct visualization of both MMM and PPP enantiomers at the single-molecule level by scanning probe microscopies.These results underline that submolecular resolution imaging by AFM/STM is a powerful real-space tool for the stereochemical characterization of 3D curved chiral nanographene structures.